%0 Journal Article
%A Ketrat, Sombat
%A Müller, Sonja
%A Dolg, Michael
%D 2007
%T A Quantum Chemical Study of the Haptotropic Rearrangements of Cr(CO)3 on
Naphthalene and Phenanthrene Systems
%U https://acs.figshare.com/articles/journal_contribution/A_Quantum_Chemical_Study_of_the_Haptotropic_Rearrangements_of_Cr_CO_sub_3_sub_on_Naphthalene_and_Phenanthrene_Systems/2996938
%R 10.1021/jp072652g.s001
%2 https://acs.figshare.com/ndownloader/files/4697950
%K substituent
%K phenanthrene complexes
%K pH value
%K haptotropic shift
%K OH
%K structure calculations
%K Characteristic points
%K Quantum Chemical Study
%K benzannulation
%K phenanthrene derivatives
%K Becke exchange
%K Perdew correlation functionals
%K energy hypersurface
%K chromium pentacarbonyl naphthylcarbene complexes
%K anthracene complexes
%K transition states
%K Cr
%K haptotropic rearrangement
%K naphthalene derivatives
%K Haptotropic Rearrangements
%X First-principles gradient-corrected density functional theory electronic structure calculations of the haptotropic
rearrangement of a Cr(CO)3 unit on naphthalene and phenanthrene derivatives are reported. Coupled-cluster
calibration studies of Cr(CO)3 complexes with benzene and naphthalene derivatives confirm the accuracy of
the applied Becke exchange and Perdew correlation functionals. Characteristic points on the energy hypersurface
(reactants, products, intermediates, and transition states) were located for various substituents on the aromatic
skeleton. It is argued that a −OH/−O- substituent may provide a means to steer the haptotropic shift depending
on the pH value, i.e., to construct a molecular switch. In addition, the mechanism of the [3 + 2 + 1]
benzannulation of chromium pentacarbonyl naphthylcarbene complexes with alkynes was investigated, and
the preference of the angular benzannulation leading to phenanthrene complexes of Cr(CO)3 over the linear
benzannulation leading to corresponding anthracene complexes is explained.
%I ACS Publications